Photocatalytic conversion of CO2 to high-value products plays a crucial role in the global pursuit of carbon-neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to navigate the photocatalytic CO2 reduction reaction(CRR).Herein,we elucidate the behaviors of isotype heterojunctions toward photocatalytic CRR over a representative photocatalyst,g-C3N4.Impressively,the isotype heterojunctions possess a significantly higher efficiency for the spatial separation and transfer of photogenerated car-riers than the single components.Along with the intrinsically outstand-ing stability,the isotype heterojunctions exhibit an exceptional and stable activity toward the CO2 photoreduction to CO.More importantly,by combining quantitative in situ technique with the first-principles modeling,we elucidate that the enhanced photoinduced charge dynamics promotes the production of key intermediates and thus the whole reaction kinetics.